Unimodal polyethylene copolymer and film thereof

ABSTRACT

A unimodal ethylene-co-1-butene copolymer that, when in melted form at 190 degrees Celsius, is characterized by a unique melt property space defined by combination of shear thinning and melt elasticity properties. A blown film consisting essentially of the unimodal ethylene-co-1-butene copolymer. A method of synthesizing the unimodal ethylene-co-1-butene copolymer. A method of making the blown film. A manufactured article comprising the unimodal ethylene-co-1-butene copolymer.

FIELD

Polyethylene copolymers, films, manufactured articles, and relatedmethods.

INTRODUCTION

Patent application publications in or about the field include US2016/0068623 A1; US 2016/0297907 A1; and WO 2017/132092 A1. Patents inor about the field include U.S. Pat. Nos. 6,989,344 B2; 7,078,467 B1;7,157,531 B2; 7,223,825 B2; 7,300,988 B2; 8,227,552 B2 and 8,497,329 B2.

SUMMARY

A unimodal ethylene-co-1-butene copolymer that, when in melted form at190 degrees Celsius (° C.), is characterized by a unique melt propertyspace defined by a combination of shear thinning and melt elasticityproperties (“the unimodal ethylene-co-1-butene copolymer”).

A method of synthesizing the unimodal ethylene-co-1-butene copolymer,the method consisting essentially of polymerizing ethylene (monomer) and1-butene (comonomer) with a single unimodal catalyst system in a singlefluidized-bed, gas phase polymerization (FB-GPP) reactor under effectiveoperating conditions, thereby making the unimodal ethylene-co-1-butenecopolymer. The “consisting essentially of” transitional phrase means themethod is free of other catalysts (i.e., is free of a multimodal orbimodal catalyst system or two or more separate catalysts), thepolymerizing is carried out in a single reactor (i.e., in the FB-GPPreactor), and the operating conditions are effective for imparting theunique combination of shear thinning and melt elasticity properties tothe unimodal ethylene-co-1-butene copolymer. Other than that, themethod's constituents and operating conditions are not particularlylimited.

A film consisting essentially of the unimodal ethylene-co-1-butenecopolymer (“the film”). The film is characterized by enhanced(increased) toughness and/or enhanced bubble stability (decreased bubbleinstability). The “consisting essentially of” transitional phrase meansthe film is free of other polyolefin polymers, but otherwise itsconstituents are not particularly limited.

A method of making a blown film, the method comprising melting theunimodal ethylene-co-1-butene copolymer to give a melt thereof,extruding the melt through a die configured for forming a bubble so asto make a bubble of the unimodal ethylene-co-1-butene copolymer, andblowing (inflating) the bubble with a film-blowing machine, therebymaking the blown film.

A manufactured article comprising the unimodal ethylene-co-1-butenecopolymer.

DETAILED DESCRIPTION

The Summary and Abstract are incorporated here by reference. Certainembodiments are described below as numbered aspects for easycross-referencing.

Aspect 1. A unimodal ethylene-co-1-butene copolymer that, when in meltedform at 190° C., is characterized by a melt property space defined by acombination of shear thinning and melt elasticity properties, whereinthe shear thinning property is defined according to equation 1 (Eq. 1):G′ (G″=3,000 Pa)<66.6*MFR5+630 (Eq. 1); and the melt elasticity propertyis defined according to equation 2 (Eq. 2): G′ (G″=3,000Pa)<23.5*SH1000+1182 (Eq. 2); wherein < is less than; * ismultiplication; / is division; = is equals; G′ (G″=3,000 Pa) is meltelasticity in Pascals (Pa) measured according to Melt Storage ModulusTest Method (described herein) at loss modulus G″=3000 pascals; MFR5 ismelt flow ratio I₂₁/I₅; I₂₁ is high-load melt index (HLMI) in grams per10 minutes (g/10 min.) measured according to ASTM D1238-13 (190° C.,21.6 kg); I₅ is melt index in g/10 min. measured according to ASTMD1238-13 (190° C., 5.0 kg); SH1000=Eta0.126/Eta126; Eta0.126 is complexviscosity in pascal-seconds (Pa-s) measured at 0.126 radian per second(rad/s) by Dynamic Mechanical Analysis Test Method (described herein);and Eta126 is complex viscosity Pa-s measured at 126 rad/s by theDynamic Mechanical Analysis Test Method. Eta0.126 may also be designatedas (η*)0.126 and Eta126 may also be designated as (η*)126. Dynamicmechanical analysis (DMA) is also known as dynamic mechanicalspectroscopy (DMS).

Aspect 2. The unimodal ethylene-co-1-butene copolymer of aspect 1wherein the melt property space is further defined by any one oflimitations (i) to (xii): (i) an I₂₁ from 13.0 to 25.0 g/10 min.,alternatively from 11.0 to 20.0 g/10 min., alternatively from 14.0 to20.0 g/10 min., measured according to ASTM D1238-13 (190° C., 21.6 kg);(ii) a MFR5 (“I₂₁/I₅”) from 20.0 to 27.0, alternatively from 20.5 to26.4, alternatively from 20.7 to 26.0, measured according to ASTMD1238-13 (190° C., 21.6 kg, “I₂₁”; and 190° C., 5.0 kg, “I₅”); (iii) anSH1000 from 35.0 to 49.0, alternatively from 35.5 to 48.0, alternativelyfrom 35.9 to 47.5, measured by the Dynamic Mechanical Analysis TestMethod; (iv) a melt storage modulus G′ (G″=3,000 Pa) value from 1900 to2300 Pa, alternatively 1950 to 2250, alternatively 1990 to 2236,measured according to the Melt Storage Modulus Test Method; (v) both (i)and (ii); (vi) both (i) and (iii); (vii) both (i) and (iv); (viii) both(ii) and (iii); (ix) both (ii) and (iv); (x) both (iii) and (iv); (xi)any three of (i) to (iv); and (xii) each of (i) to (iv).

Aspect 3. The unimodal ethylene-co-1-butene copolymer of aspect 1 or 2characterized by any one of limitations (i) to (xvii): (i) a densityfrom 0.9410 to 0.9550 gram per cubic centimeter (g/cm³), alternatively0.9450 to 0.9530 g/cm³, alternatively 0.9480 to 0.9500 g/cm³, measuredaccording to ASTM D792-13, Method B; (ii) a weight-average molecularweight (M_(w)) from 200,000.0 to 400,000.0 grams per mole (g/mol),alternatively 250,000.0 to 350,000.0 g/mol, alternatively 260,000.0 to310,000.0 g/mol, measured according to the Gel Permeation Chromatography(GPC) Test Method; (iii) a number-average molecular weight (M_(n)) from11,000.0 to 14,000.0 g/mol, alternatively 11,800.0 to 13,200.0 g/mol,alternatively 11,950 to 12,890 g/mol, measured according to the GPC TestMethod; (iv) a z-average molecular weight (M_(z)) from 2,400,000 to3,600,000 g/mol, measured according to the GPC Test Method; (v) amolecular mass dispersity (M_(w)/M_(n)), Ð_(M)′ from 20.0 to 26.0,alternatively from 20.45 to 25.94, alternatively from 20.50 to 25.90,wherein M_(w) and M_(n) are measured according to the GPC Test Method;(vi) both (i) and (ii); (vii) both (i) and (iii); (viii) both (i) and(iv); (ix) both (i) and (v); (x) both (ii) and (iii); (xi) both (ii) and(iv); (xii) both (ii) and (v); (xiii) both (iii) and (iv); (xiv) both(iii) and (v); (xv) both (iv) and (v); (xvi) any four of (i) to (v); and(xvii) each of (i) to (v).

Aspect 4. The unimodal ethylene-co-1-butene copolymer of any one ofaspects 1 to 3 that, when in the form of a blown film and having athickness of 0.0127 millimeter (mm, 0.500 mil), is characterized by anyone of limitations (i) to (xii): (i) a dart impact from 115 to 139 grams(g), alternatively 118 to 136 g, alternatively 119 to 135 g, measuredaccording to the Dart Impact Test Method; (ii) an Elmendorf tear incross direction (CD) from 40.0 to 160.0 gram-force (gf), alternatively45 to 159 gf, alternatively 46 to 155 gf, measured according to theElmendorf Tear Test Method; (iii) an Elmendorf tear in machine direction(MD) from 10.0 to 250.0 gf, alternatively 12 to 23 gf, alternatively 13to 22 gf, measured according to the Elmendorf Tear Test Method; (iv) abubble stability rating of Good, measured according to the BubbleStability Test Method; (v) both (i) and (ii); (vi) both (i) and (iii);(vii) both (i) and (iv); (viii) both (ii) and (iii); (ix) both (ii) and(iv); (x) both (iii) and (iv); (xi) any two of (i) to (iii); and (xii)each of (i) to (iii).

Aspect 5. A method of synthesizing the unimodal ethylene-co-1-butenecopolymer of any one of aspects 1 to 4, the method consistingessentially of contacting ethylene and 1-butene with a single catalystsystem consisting of a unimodal chromium catalyst system in a singlefluidized bed, gas-phase polymerization (FB-GPP) reactor under effectiveoperating conditions comprising a reactor bed temperature (RBT), anaverage polymer residence time (avgPRT), and an ethylene partialpressure (C2P) and receiving an ethylene (C₂) feed, a comonomer (C₄)feed, a hydrogen (H₂) feed, and, optionally, an oxygen (O₂) feed whereinthe feeds are characterized by a H₂/C₂ gas molar ratio (H₂/C₂), acomonomer/ethylene gas molar ratio (“C₄/C₂”), and a O₂/C₂ gas volumeratio (“[O₂/C₂]”, vol/vol in ppmv); wherein RBT is from 101° to 111° C.;avgPRT is from 1.70 to 3.10 hours, C2P is from 1,100 to 1,900kilopascals (kPa); H₂/C₂ gas molar ratio is from 0.01 to 0.110; C₄/C₂gas molar ratio is from 0.010 to 0.021, alternatively from 0.011 to0.0205, alternatively from 0.0150 to 0.0202; and O₂/C₂ gas volume ratiois from >0 to 90 parts per billion volume/volume (ppbv), alternativelyfrom 30 to 80 ppbv, alternatively from 31 to 79 ppbv; therebysynthesizing the unimodal ethylene-co-1-butene copolymer in the FB-GPPreactor. The H₂/O₂ gas molar ratio, C₄/O₂ gas molar ratio, and O₂/C₂ gasvolume ratio are determined by measuring (e.g., metering) the amounts ofH₂, O₂, O₄ and O₂ gases being fed into the FB-GPP reactor. The reactorbed temperature RBT and the H₂/O₂ gas molar ratio are useful in themethod of synthesizing the unimodal ethylene-co-1-butene copolymer that,when in melt form at 190° C., satisfies Eq. 1 and Eq. 2 describedearlier. The “consisting essentially of” transitional phrase means themethod is free of other catalysts (i.e., is free of a multimodal orbimodal catalyst system or two or more separate catalysts), thepolymerizing is carried out in a single reactor (i.e., in the FB-GPPreactor), and the operating conditions are effective for imparting theunique combination of shear thinning and melt elasticity properties tothe unimodal ethylene-co-1-butene copolymer. Other than that, themethod's constituents and operating conditions are not particularlylimited. The unimodal chromium catalyst system and its preparation aredescribed herein. The unimodal chromium catalyst system may be a reducedchromium oxide catalyst system, which along with its preparation aredescribed herein. The reduced chromium oxide catalyst system may beACCLAIM™ K-100 advanced chrome catalyst (described herein), availablefrom Univation Technologies LLC, Houston, Tex., USA.

Aspect 6. The method of aspect 5 further comprising removing theunimodal ethylene-co-1-butene copolymer from the FB-GPP reactor to givea removed unimodal ethylene-co-1-butene copolymer. In some aspects theremoved unimodal ethylene-co-1-butene copolymer may be purged with aninert gas (e.g., N₂) to remove entrained hydrocarbons therefrom and/ortreated with a stream of humidified nitrogen (N₂) gas to deactivate insitu any residual amount of the reduced chromium oxide catalyst systemtherein. In some aspects the removed unimodal ethylene-co-1-butenecopolymer is pelletized to give pellets of the removed unimodalethylene-co-1-butene copolymer. In some aspects the removed unimodalethylene-co-1-butene copolymer may be combined with one or more filmadditives useful in polyethylene films. The combining may comprisingmelt mixing the one or more film additives into a melt of the removedunimodal ethylene-co-1-butene copolymer. Alternatively the combining maycomprise soaking or injecting the one or more film additives into thepellets of the removed unimodal ethylene-co-1-butene copolymer.

Aspect 7. A manufactured article comprising the unimodalethylene-co-1-butene copolymer of any one of aspects 1 to 4.

Aspect 8. A film consisting essentially of the unimodalethylene-co-1-butene copolymer of any one of aspects 1 to 4 (“thefilm”). The “consisting essentially of” transitional phrase means thefilm is free of other polyolefin polymers, but otherwise itsconstituents are not particularly limited. The film may be used inpackaging applications to protect a substance in need of covering,wherein the film is disposed to at least partially cover the substance.Examples of substances in need of covering are paper, paperboard (e.g.,cardboard), food, pharmaceutical compounds, and a stack of paperboardboxes (e.g., wherein the film is a shrink wrap used for wrapping apallet stacked with paperboard boxes). In some aspects the film is ablown film made as described below.

Aspect 9. A method of making a blown film, the method comprising meltingthe unimodal ethylene-co-1-butene copolymer of any one of aspects 1 to 4so as to give a melt thereof, extruding the melt through a dieconfigured for forming a bubble so as to make a bubble of the unimodalethylene-co-1-butene copolymer, and blowing (inflating) the bubble witha film-blowing machine, thereby making the blown film, which isrestricted in one dimension. The bubble is restricted in one dimension.The blown film may be made or fabricated without internal bubble cooling(IBC) by any suitable method, including high stalk film blowing withoutIBC, such as by using a high stalk film blowing manufacturing linewithout (active) IBC equipment. The blown film consists essentially ofthe unimodal ethylene-co-1-butene copolymer of any one of aspects 1 to 4(“the blown film”). The “consisting essentially of” transitional phrasemeans the blown film is free of other polyolefin polymers, but otherwiseits constituents are not particularly limited.

Embodiments of the blown film may optionally contain zero, one or morefilm additives. The “film additive” is a compound or material other thana polyolefin polymer that imparts one or more properties to, and/orenhances one or more properties of, the blown film. Examples of filmadditives are antimicrobial agents, antioxidants, catalyst neutralizers(of chromium-based catalysts), colorants, and light stabilizers. Thefilm additive(s), when present, may be pre-mixed with the unimodalethylene-co-1-butene copolymer prior to the melting step in the methodof making the blown film. Alternatively, film additive(s), when present,may be added to the melt of the unimodal ethylene-co-1-butene copolymerduring or after the melting step and prior to the extruding step in themethod of making the blown film. When two or more film additives areused, one or more film additives may be pre-mixed with the unimodalethylene-co-1-butene copolymer prior to the melting step in the methodof making the blown film and a one or more film additives may be addedto the melt of the unimodal ethylene-co-1-butene copolymer during orafter the melting step and prior to the extruding step in the method ofmaking the blown film. In some aspects the blown film consistsessentially of the unimodal ethylene-co-1-butene copolymer, at least oneantioxidant, and at least one catalyst neutralizer (of chromium-basedcatalysts). Examples of the at least one antioxidant and at least onecatalyst neutralizer are described herein.

Aspect 10. A blown film made by the method of aspect 9 and consistingessentially of the unimodal ethylene-co-1-butene copolymer of any one ofaspects 1 to 4 (“the blown film”). The “consisting essentially of”transitional phrase means the blown film is free of other polyolefinpolymers, but otherwise its constituents are not particularly limited.The blown film is characterized by enhanced (increased) bubblestability, i.e., decreased bubble instability. The blown film optionallymay contain zero, one or more of the film additives. The blown film maybe characterized by enhanced (increased) toughness and/or enhancedbubble stability (decreased bubble instability). The blown film may beused in the packaging applications.

The unimodal ethylene-co-1-butene copolymer may be generally describedas a medium molecular weight high density polyethylene (MMW HDPE).

The unimodal ethylene-co-1-butene copolymer, films, and method of makingthe unimodal ethylene-co-1-butene copolymer are free of Ziegler-Nattacatalysts, metallocene catalysts, and post-metallocene catalysts. E.g.,free of Ti, Hf, Zr metals.

Definitions

As used herein, bubble stability is measured according to the methodsdescribed herein.

Catalyst. A material that enhances rate of a reaction (e.g., thepolymerization of ethylene and 1-butene) and is not completely consumedthereby.

Catalyst system. A combination of a catalyst per se and a companionmaterial such as a modifier compound for attenuating reactivity of thecatalyst, a support material on which the catalyst is disposed, acarrier material in which the catalyst is disposed, or a combination ofany two or more thereof, or a reaction product of a reaction of thecatalyst per se and the companion material.

Consisting essentially of, consist(s) essentially of, and the like.Partially-closed ended expressions that exclude anything that wouldaffect the basic and novel characteristics of that which they describe,but otherwise allow anything else. In some aspects any one,alternatively each “comprising” or “comprises” may be replaced by“consisting essentially of” or “consists essentially of”, respectively;alternatively by “consisting of” or “consists of”, respectively.

Consisting of and consists of. Closed ended expressions that excludeanything that is not specifically described by the limitation that itmodifies. In some aspects any one, alternatively each expression“consisting essentially of” or “consists essentially of” may be replacedby the expression “consisting of” or “consists of”, respectively.

Dry. Generally, a moisture content from 0 to less than 5 parts permillion based on total parts by weight. Materials fed to the reactor(s)during a polymerization reaction are dry.

Feeds. Quantities of reactants and/or reagents that are added or “fed”into a reactor. In continuous polymerization operation, each feedindependently may be continuous or intermittent. The quantities or“feeds” may be measured, e.g., by metering, to control amounts andrelative amounts of the various reactants and reagents in the reactor atany given time.

Film: an article restricted in one dimension. The restricted dimensionmay be called a thickness of the film, and the thickness issubstantially uniform therein. Claimed film properties are measured on13 (12.7) micrometers thick monolayer films.

Inert. Generally, not (appreciably) reactive or not (appreciably)interfering therewith in the inventive polymerization reaction. The term“inert” as applied to the purge gas or ethylene feed means a molecularoxygen (O₂) content from 0 to less than 5 parts per million based ontotal parts by weight of the purge gas or ethylene feed.

Internal bubble cooling or IBC is an aspect of film blowing performed byactively using ancillary, special purpose IBC equipment such as that ofUS 2002/0150648 A1 to R. E. Cree.

Metallocene catalysts. Substantially single site or dual site catalyticmolecules based on metal-cyclopentadienyl ligand complexes.

Post-metallocene catalysts. Substantially single site or dual sitecatalytic molecules based on metal-ligand complexes wherein the ligandis a substituted cyclopentadienyl or multidentate molecular anion.

Unimodal. When referring to a polymer: having a single peak (noshoulder) in a plot of dW/d Log(MW) on the y-axis versus Log(MW) on thex-axis to give a Gel Permeation Chromatograph (GPC) chromatogram,wherein Log(MW) and dW/d Log(MW) are as defined herein and are measuredby Gel Permeation Chromatograph (GPC) Test Method described herein. Whenreferring to a catalyst or catalyst system: producing a unimodalpolymer.

Ziegler-Natta catalysts. Heterogeneous materials that enhance olefinpolymerization reaction rates and typically are products that areprepared by contacting inorganic titanium compounds, such as titaniumhalides supported on a magnesium chloride support, with an activator.

Melt elasticity of a thermoplastic polymer can be thought of as thebehavior of a melt of the polymer during a shaping process such asextrusion or film formation. It is one of the determinants ofviscoelastic melt behavior, wherein viscosity decreases with increasingshear rate. Unsatisfactory melt elasticity may undesirably cause dieswell during extrusion or problems with bubble stability during filmblowing. A measure of, or proxy for, melt elasticity used herein is amelt storage modulus (G′) value that is measured using DMA (DynamicMechanical Analysis) on polymer melts at 190° C. by performingsmall-strain (10%) oscillatory shear at varying frequency from 0.02radian per second (rad/s) to about 200 rad/s using an ARES-G2 AdvancedRheometric Expansion System, from TA Instruments, with parallel-plategeometry to obtain the G′ (G″=3,000 Pa) value in pascals of melt storagemodulus (G′) at a dynamic frequency where loss modulus (G″) is equal to3,000 Pascals.

Polymerization Method

In an illustrative pilot plant process for making the unimodalethylene-co-1-butene copolymer, a fluidized bed, gas-phasepolymerization reactor (“FB-GPP reactor”) having a reaction zonedimensioned as 304.8 mm (twelve inch) internal diameter and a 2.4384meter (8 feet) in straight-side height and containing a fluidized bed ofgranules of the unimodal ethylene-co-1-butene copolymer. Configure theFB-GPP reactor with a recycle gas line for flowing a recycle gas stream.Fit the FB-GPP reactor with gas feed inlets and polymer product outlet.Introduce gaseous feed streams of ethylene and hydrogen together withcomonomer (e.g., 1-butene) below the FB-GPP reactor bed into the recyclegas line. Control individual flow rates of ethylene (“C₂”), hydrogen(“H₂”) and 1-butene or “C₄”) to maintain a fixed comonomer to ethylenemonomer gas molar ratio (C_(x)/C₂, e.g., C₄/C₂) equal to a describedvalue (e.g., 0.0050), a constant hydrogen to ethylene gas molar ratio(“H2/C2”) equal to a described value (e.g., 0.0020), and a constantethylene (“C₂”) partial pressure equal to a described value (e.g., 1,000kPa). Measure concentrations of all gases by an in-line gaschromatograph to understand and maintain composition in the recycle gasstream. Maintain a reacting bed of growing polymer particles in afluidized state by continuously flowing a make-up feed and recycle gasthrough the reaction zone. Use a superficial gas velocity of 0.49 to0.67 meter per second (m/sec) (1.6 to 2.2 feet per second (ft/sec)).Operate the FB-GPP reactor at a total pressure of about 2344 to about2413 kilopascals (kPa) (about 340 to about 350 pounds per squareinch-gauge (psig)) and at a described first reactor bed temperature RBT(e.g., 105° C.). Maintain the fluidized bed at a constant height bywithdrawing a portion of the bed at a rate equal to the rate ofproduction of particulate form of the unimodal ethylene-co-1-butenecopolymer, which production rate may be from 10 to 20 kilograms per hour(kg/hr), alternatively 13 to 18 kg/hr. Remove the product unimodalethylene-co-1-butene copolymer semi-continuously via a series of valvesinto a fixed volume chamber, wherein this removed unimodalethylene-co-1-butene copolymer is purged to remove entrainedhydrocarbons and treated with a stream of humidified nitrogen (N₂) gasto deactivate any trace quantities of residual catalyst. Seepolymerization method described herein.

Polymerization or operating conditions are any variable or combinationof variables that may affect a polymerization reaction in the GPPreactor or a composition or property of an unimodal ethylene-co-1-butenecopolymer product made thereby. The variables may include reactor designand size, catalyst composition and amount; reactant composition andamount; molar ratio of two different reactants; presence or absence offeed gases such as H₂ and/or O₂, molar ratio of feed gases versusreactants, absence or concentration of interfering materials (e.g.,H₂O), absence or presence of an induced condensing agent (ICA), averagepolymer residence time in the reactor, partial pressures ofconstituents, feed rates of monomers, reactor bed temperature (e.g.,fluidized bed temperature), nature or sequence of process steps, timeperiods for transitioning between steps. Variables other than that/thosebeing described or changed by the method or use may be kept constant.

Comonomer/ethylene gas molar ratio C_(x)/C₂ of comonomer (1-butene, O₄)and ethylene being fed into the gas-phase polymerization (GPP) reactormay be from 0.0001 to 0.1, alternatively from 0.0002 to 0.05,alternatively from 0.0004 to 0.02.

Gas molar ratio of comonomer to ethylene (“C_(x)/C₂ gas molar ratio”) isthe quantity of all alpha-olefin comonomer(s) (“C_(x)”), in moles, beingfed in a gaseous or vaporous state into the GPP reactor divided by thequantity of ethylene monomer (O₂), in moles, being fed in a gaseousstate into the GPP reactor. The moles of comonomer and moles of ethyleneused to calculate the C_(x)/C₂ gas molar ratio values are measured bygas flow meters or other suitable means.

Ethylene partial pressure (e.g., C2P) in the GPP reactor. From 690 to2070 kilopascals (kPa, i.e., from 100 to 300 psia (pounds per squareinch absolute)); alternatively from 830 to 1655 kPa (120 to 240 psia),alternatively from 1300 to 1515 kPa (190 to 220 psia). Alternatively,the partial pressure of ethylene may be from 690 to 3450 kilopascals(kPa, 100 to 500 pounds per square inch absolute (psia)), alternatively1030 to 2070 kPa (150 to 300 psia), alternatively 1380 to 1720 kPa (200to 250 psia), alternatively 1450 to 1590 kPa (210 to 230 psia), e.g.,1520 kPa (220 psia). 1.000 psia=6.8948 kPa.

Hydrogen to ethylene (H₂/O₂) gas molar ratio in the GPP reactor is from0.010 to 0.100, alternatively from 0.011 to 0.094.

Induced condensing agent (ICA). An inert liquid useful for coolingmaterials in the polymerization reactor(s) (e.g., a fluidized bedreactor). In some aspects the ICA is a (C₅-C₂₀)alkane, alternatively a(C₁₁-C₂₀)alkane, alternatively a (C₅-C₁₀)alkane. In some aspects the ICAis a (C₅-C₁₀)alkane. In some aspects the (C₅-C₁₀)alkane is a pentane,e.g., normal-pentane or isopentane; a hexane; a heptane; an octane; anonane; a decane; or a combination of any two or more thereof. In someaspects the ICA is isopentane (i.e., 2-methylbutane). The inventivemethod of polymerization, which uses the ICA, may be referred to hereinas being an induced condensing mode operation (ICMO). Concentration ingas phase measured using gas chromatography by calibrating peak areapercent to mole percent (mol %) with a gas mixture standard of knownconcentrations of ad rem gas phase components. Concentration may be from1 to 10 mol %, alternatively from 3 to 8 mole %.

Oxygen (O₂) concentration relative to ethylene (“[O₂/C₂]”, volume partsO₂ per million volume parts ethylene (ppmv)) in the GPP reactor. In someembodiments the [O₂/C₂] is from 0.0000 to 0.20 ppmv, alternatively from0.0001 to 0.200 ppmv, alternatively from 0.0000 to 0.183 ppmv,alternatively from 0.0000 to 0.163 ppmv.

The polymerization method uses a gas-phase polymerization (GPP) reactor,such as a stirred-bed gas phase polymerization reactor (SB-GPP reactor)or a fluidized-bed gas-phase polymerization reactor (FB-GPP reactor), tomake the unimodal ethylene-co-1-butene copolymer. Such reactors andmethods are generally well-known in the art. For example, the GPPreactor/method may employ the induced condensing agent and be conductedin condensing mode polymerization such as described in U.S. Pat. Nos.4,453,399; 4,588,790; 4,994,534; 5,352,749; 5,462,999; and 6,489,408.The GPP reactor/method may be a fluidized-bed gas-phase polymerizationreactor (FB-GPP reactor)/method as described in U.S. Pat. Nos.3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400;5,352,749; 5,541,270; EP-A-0 802 202; and Belgian Patent No. 839,380.These SB-GPP and FB-GPP polymerization reactors and processes eithermechanically agitate or fluidize by continuous flow of gaseous monomerand diluent the polymerization medium inside the reactor, respectively.Other reactors/processes contemplated include series or multistagepolymerization processes such as described in U.S. Pat. Nos. 5,627,242;5,665,818; 5,677,375; EP-A-0 794 200; EP-B1-0 649 992; EP-A-0 802 202;and EP-B-634421.

The polymerization conditions may further include one or more additivessuch as a chain transfer agent, a promoter, or a scavenging agent. Thechain transfer agents are well known and may be alkyl metal such asdiethyl zinc. Promoters are known such as in U.S. Pat. No. 4,988,783 andmay include chloroform, CFCl₃, trichloroethane, anddifluorotetrachloroethane. Scavenging agents may be a trialkylaluminum.Gas phase polymerizations may be operated free of (not deliberatelyadded) scavenging agents. The polymerization conditions for gas phasepolymerization reactor/method may further include an amount (e.g., 0.5to 200 ppm based on all feeds into reactor) of a static control agentand/or a continuity additive such as aluminum stearate orpolyethyleneimine. The static control agent may be added to the FB-GPPreactor to inhibit formation or buildup of static charge therein.

Start-up or restart of the GPP reactor may be illustrated with afluidized bed, GPP reactor. The start-up of a recommissioned FB-GPPreactor (cold start) or restart of a transitioning FB-GPP reactor (warmstart) includes a time period that is prior to reaching steady-statepolymerization conditions of step (a). Start-up or restart may includethe use of a polymer seedbed preloaded or loaded, respectively, into thefluidized bed reactor. The polymer seedbed may be composed of powder ofa polyethylene such as a polyethylene homopolymer or previously madebatch of the unimodal ethylene-co-1-butene copolymer.

Start-up or restart of the FB-GPP reactor may also include gasatmosphere transitions comprising purging air or other unwanted gas(es)from the reactor with a dry (anhydrous) inert purge gas, followed bypurging the dry inert purge gas from the FB-GPP reactor with dryethylene gas. The dry inert purge gas may consist essentially ofmolecular nitrogen (N₂), argon, helium, or a mixture of any two or morethereof. When not in operation, prior to start-up (cold start), theFB-GPP reactor contains an atmosphere of air. The dry inert purge gasmay be used to sweep the air from a recommissioned FB-GPP reactor duringearly stages of start-up to give a FB-GPP reactor having an atmosphereconsisting of the dry inert purge gas. Prior to restart (e.g., after achange in seedbeds), a transitioning FB-GPP reactor may contain anatmosphere of unwanted ICA or other unwanted gas or vapor. The dry inertpurge gas may be used to sweep the unwanted vapor or gas from thetransitioning FB-GPP reactor during early stages of restart to give theFB-GPP reactor an atmosphere consisting of the dry inert purge gas. Anydry inert purge gas may itself be swept from the FB-GPP reactor with thedry ethylene gas. The dry ethylene gas may further contain molecularhydrogen gas such that the dry ethylene gas is fed into the fluidizedbed reactor as a mixture thereof. Alternatively the dry molecularhydrogen gas may be introduced separately and after the atmosphere ofthe fluidized bed reactor has been transitioned to ethylene. The gasatmosphere transitions may be done prior to, during, or after heatingthe FB-GPP reactor to the reaction temperature of the polymerizationconditions.

Start-up or restart of the FB-GPP reactor also includes introducingfeeds of reactants and reagents thereinto. The reactants include theethylene and the alpha-olefin. The reagents fed into the fluidized bedreactor include the molecular hydrogen gas and the induced condensingagent (ICA) and the chromium-based catalyst system (e.g., ACCLAIM™ K-100advanced chrome catalyst).

In an embodiment the method uses a pilot scale fluidized bed gas phasepolymerization reactor (Pilot Reactor) that comprises a reactor vesselcontaining a fluidized bed of a powder of the unimodalethylene-co-1-butene copolymer, and a distributor plate disposed above abottom head, and defining a bottom gas inlet, and having an expandedsection, or cyclone system, at the top of the reactor vessel to decreaseamount of resin fines that may escape from the fluidized bed. Theexpanded section defines a gas outlet. The Pilot Reactor furthercomprises a compressor blower of sufficient power to continuously cycleor loop gas around from out of the gas outlet in the expanded section inthe top of the reactor vessel down to and into the bottom gas inlet ofthe Pilot Reactor and through the distributor plate and fluidized bed.The Pilot Reactor further comprises a cooling system to remove heat ofpolymerization and maintain the fluidized bed at a target temperature.Compositions of gases such as ethylene, alpha-olefin, hydrogen, andoxygen being fed into the Pilot Reactor are monitored by an in-line gaschromatograph in the cycle loop in order to maintain specificconcentrations that define and enable control of polymer properties. Insome embodiments the gases are cooled, resulting in their temperaturedropping below their dew point, at which time the Pilot Reactor is incondensing mode operation (CMO) or induced condensing mode operation(ICMO). In CMO, liquids are present downstream of the cooler and in thebottom head below the distributor plate. The chromium-based catalystsystem (e.g., ACCLAIM™ K-100 advanced chrome catalyst) may be fed as aslurry or dry powder into the Pilot Reactor from high pressure devices,wherein the slurry is fed via a syringe pump and the dry powder is fedvia a metered disk. The chromium-based catalyst system typically entersthe fluidized bed in the lower ⅓ of its bed height. The Pilot Reactorfurther comprises a way of weighing the fluidized bed and isolationports (Product Discharge System) for discharging the powder of unimodalethylene-co-1-butene copolymer from the reactor vessel in response to anincrease of the fluidized bed weight as polymerization reactionproceeds.

In some embodiments the FB-GPP reactor is a commercial scale reactorsuch as a UNIPOL™ reactor or UNIPOL™ II reactor, which are availablefrom Univation Technologies, LLC, a subsidiary of The Dow ChemicalCompany, Midland, Mich., USA.

Chromium-Based Catalyst System

The chromium-based catalyst system (e.g., ACCLAIM™ K-100 advanced chromecatalyst) is unimodal and comprises a reduced chromium oxide catalystcompound and, optionally, one or more of a modifying agent, a reducingagent, an activator, and a support material. The reduced chromium oxidecatalyst compound may comprise or be a reaction product be prepared froman activated chromium oxide catalyst compound and a reducing agent,optionally modified by a silyl chromate catalyst compound. Thechromium-based catalyst system may be unsupported, that is free of asupport material. The support material differs from the activator andthe chromium-based catalyst compound in at least one of function (e.g.,reactivity), composition (e.g., metal content), and property such asporosity. Alternatively, the chromium-based catalyst system may furthercomprise a support material for hosting the chromium-based catalystcompound and/or an activator. The chromium-based catalyst compound ofthe chromium-based catalyst system may be activated by any suitablemethod, which may or may not employ an activator, and under any suitableactivating conditions, as described herein.

The chromium oxide catalyst compound comprises CrO₃ or any chromiumcompound convertible to CrO₃ under catalyst activating conditions.Compounds convertible to CrO₃ are disclosed in, for example, U.S. Pat.Nos. 2,825,721; 3,023,203; 3,622,251; and 4,011,382. Examples arechromic acetyl acetonate, chromic halide, chromic nitrate, chromicacetate, chromic sulfate, ammonium chromate, ammonium dichromate, andother soluble, chromium containing salts. Chromium oxide catalystcompounds include Philips-type catalyst compounds, commonly referred toas “inorganic oxide-supported Cr⁺⁶” catalysts. A Philips-type catalystcompound may be formed by a process that includes impregnating a Cr⁺³compound into a silica support, followed by calcining the impregnatedsilica support under oxidizing conditions at 300° to 900° C.,alternatively, 400° to 860° C. to give the Philips-type catalystcompound. Under these conditions, at least some of the Cr⁺³ areconverted to Cr⁺⁶.

The silyl chromate catalyst compound may be a bis(trihydrocarbylsilyl)chromate or a poly(diorganosilyl) chromate. The bis(trihydrocarbylsilyl)chromate may be bis(triethylsilyl) chromate, bis(tributylsilyl)chromate, bis(triisopentylsilyl) chromate, bis(tri-2-ethylhexylsilyl)chromate, bis(tridecylsilyl) chromate, bis(tri(tetradecyl)silyl)chromate, bis(tribenzylsilyl) chromate, bis(triphenylethylsilyl)chromate, bis(triphenylsilyl) chromate, bis(tritolylsilyl) chromate,bis(trixylylsilyl) chromate, bis(trinaphthylsilyl) chromate,bis(triethylphenylsilyl) chromate, or bis(trimethylnaphthylsilyl)chromate. The poly(diorganosilyl) chromate may be polydiphenylsilylchromate or polydiethylsilyl chromate. In some embodiments, the silylchromate compound is bis(triphenylsilyl) chromate, bis(tritolylsilyl)chromate, bis(trixylylsilyl) chromate, or bis(trinaphthylsilyl)chromate; alternatively bis(triphenylsilyl) chromate. See U.S. Pat. Nos.3,324,101; 3,704,287; and 4,100,105.

Supported catalyst compounds. The chromium-based catalyst compound, suchas the chromium oxide catalyst compound, the silyl chromate catalystcompound, and/or the reduced chromium oxide catalyst compound,independently may be unsupported, i.e., free of a support material.Alternatively, the chromium-based catalyst compound, such as thechromium oxide catalyst compound, the silyl chromate catalyst compound,or the reduced chromium oxide catalyst compound, may be disposed on asupport material. That is, the chromium-based catalyst system maycomprise the chromium-based catalyst compound and support material.Typically, the supported reduced chromium oxide catalyst compound ismade in situ by contacting a pre-activated and supported chromium oxidecatalyst compound, optionally modified with a silyl chromate catalystcompound, with a reducing agent to give an activated and supportedreduced chromium oxide catalyst compound.

Support material. The support material may be an inorganic oxidematerial. The terms “support” and “support material” are the same asused herein and refer to a porous inorganic substance or organicsubstance. In some embodiments, desirable support materials may beinorganic oxides that include Group 2, 3, 4, 5, 13 or 14 oxides,alternatively Group 13 or 14 atoms. Examples of inorganic oxide-typesupport materials are silica, alumina, titania, zirconia, thoria, andmixtures of any two or more of such inorganic oxides. Examples of suchmixtures are silica-chromium, silica-alumina, and silica-titania.

The inorganic oxide support material is porous and has variable surfacearea, pore volume, and average particle size. In some embodiments, thesurface area is from 50 to 1000 square meter per gram (m²/g) and theaverage particle size is from 20 to 300 micrometers (μm). Alternatively,the pore volume is from 0.5 to 6.0 cubic centimeters per gram (cm³/g)and the surface area is from 200 to 600 m²/g. Alternatively, the porevolume is from 1.1 to 1.8 cm³/g and the surface area is from 245 to 375m²/g. Alternatively, the pore volume is from 2.4 to 3.7 cm³/g and thesurface area is from 410 to 620 m²/g. Alternatively, the pore volume isfrom 0.9 to 1.4 cm³/g and the surface area is from 390 to 590 m²/g. Eachof the above properties are measured using conventional techniques knownin the art.

The support material may comprise silica, alternatively amorphous silica(not quartz), alternatively a high surface area amorphous silica (e.g.,from 500 to 1000 m²/g). Such silicas are commercially available from anumber of sources including the Davison Chemical Division of W.R. Graceand Company (e.g., Davison 952 and Davison 955 products), and PQCorporation (e.g., ES70 product). The silica may be in the form ofspherical particles, which are obtained by a spray-drying process.Alternatively, MS3050 product is a silica from PQ Corporation that isnot spray-dried. As procured, all of these silicas are not calcined(i.e., not dehydrated). Silica that is calcined prior to purchase mayalso be used as the support material.

Supported chromium compounds, such as, for example, supported chromiumacetate, are commercially available and may be used as an embodiment ofthe chromium-based catalyst system. Commercial examples include Davison957, Davison 957HS, and Davison 957BG products from Davison ChemicalDivision, and ES370 product from PQ Corp. The supported chromiumcompound may in the form of spherical particles, which are obtained by aspray-drying process. Alternatively, C35100MS and C35300MS products fromPQ Corporation are not spray-dried. As procured, all of these silicasare not activated. Supported chromium compounds that are activated priorto purchase may be used as the supported chromium compound.

Prior to being contacted with a chromium oxide catalyst compound, thesupport material may be pre-treated by heating the support material inair to give a calcined support material. The pre-treating comprisesheating the support material at a peak temperature from 350° to 850° C.,alternatively from 400° to 800° C., alternatively from 400° to 700° C.,alternatively from 500° to 650° C. and for a time period from 2 to 24hours, alternatively from 4 to 16 hours, alternatively from 8 to 12hours, alternatively from 1 to 4 hours, thereby making a calcinedsupport material. In some aspects the support material is a calcinedsupport material.

In some embodiments the supported chromium oxide catalyst system furthercomprises a silyl chromate compound as a modifying agent. As such, thesilyl chromate compound may be added to a slurry of the activated(unsupported or supported) chromium oxide catalyst system in a non-polaraprotic solvent to give a slurry of a modified activated supportedchromium oxide catalyst system. The solvent may be removed by heating,optionally under reduced pressure, according to the drying processdescribed herein.

Catalyst activation. Any one of the foregoing chromium oxide catalystcompounds or silyl chromate catalyst compound, whether unsupported orsupported on an uncalcined or calcined support material, independentlymay be activated by heating in an oxidative environment (e.g.,well-dried air or oxygen) at an activation temperature of from 300° C.or higher with the proviso that the maximum activation temperature isbelow that at which substantial sintering of the compounds and/orsupport material would occur. The activating gives an activated(unsupported or supported) chromium oxide catalyst compound and/or anactivated (unsupported or supported) silyl chromate catalyst compound.For example to activate the Philips catalyst, a fluidized bed of thesupported chromium oxide catalyst compound may be activated by passing astream of dry air or oxygen therethrough, thereby displacing any watertherefrom and converting at least some Cr⁺³ compound to Cr⁺⁶ compound.The maximum activation temperature may be from 300° to 900° C.,alternatively 400° to 850° C., alternatively from 500° to 700° C.,alternatively from 550° to 650° C. The activation time period may befrom 1 to 48 hours, alternatively from 1 to 36 hours, alternatively from3 to 24 hours, alternatively from 4 to 6 hours. All other things beingequal, the higher the activation temperature used, the shorter theactivation period of time to achieve a given level of activation, andvice versa. The resulting activated (unsupported or supported) chromiumoxide catalyst system may be in the form of a powdery, free-flowingparticulate solid.

The reduced chromium oxide catalyst compound. An activated (unsupportedor supported) reduced chromium oxide catalyst compound and system may beprepared from the activated (unsupported or supported) chromium oxidecatalyst system. In one embodiment, the activated (unsupported orsupported) chromium oxide catalyst system has been prepared from acalcined support material. The activated (unsupported or supported)chromium oxide catalyst system may be unmodified, alternatively may havebeen modified by the silyl chromate compound according to the modifyingmethod described earlier. The preparing comprises agitating a slurry ofthe activated (unsupported or supported) chromium oxide catalyst systemin a non-polar, aprotic solvent under an inert atmosphere, adding areducing agent to the agitated slurry over a period of time (additiontime), and then allowing the resulting reaction mixture to react underthe inert atmosphere for a period of time (reaction time) to make theactivated (unsupported or supported) reduced chromium oxide catalystcompound and system, which typically is supported on the supportmaterial, as a slurry in the non-polar, aprotic solvent. The inertatmosphere may comprise anhydrous N₂ gas, Ar gas, He gas, or a mixturethereof. The inert atmosphere may be at a pressure from 101 to 700kilopascals (kPa). The temperature of the agitated slurry during theadding step may be from 30° to 80° C., alternatively from 40° to 60° C.The agitation may be performed at a rate less than 70 rotations perminute (rpm) and the addition time may be less than 20 minutes.Alternatively, the agitation rate may be greater than 70 rpm and theaddition time may be less than 20 minutes. Alternatively, the agitationrate may be greater than 70 rpm and the addition time may be greaterthan 20 minutes. The agitation rate may be from 30 to 50 rpm, and theaddition time may be from 20 to 80 minutes. The temperature of thereaction mixture during the allowing step may be from 20° to 80° C.,alternatively from 20° to 60° C., alternatively from 20° to 40° C. Thereaction time period may be from 0.08 to 2 hours.

The reducing agent may be an organoaluminum compound, such as analuminum alkyl or an alkyl aluminum alkoxide. The alkyl aluminumalkoxide may be of formula R₂AlOR, wherein each R is independently anunsubstituted (C₁-C₁₂)alkyl group, alternatively unsubstituted(C₁-C₁₀)alkyl group, alternatively unsubstituted (C₂-C₈)alkyl group,alternatively unsubstituted (C₂-C₄)alkyl group. Examples of the alkylaluminum alkoxides are diethyl aluminum methoxide, diethyl aluminumethoxide, diethyl aluminum propoxide, dimethyl aluminum ethoxide,di-isopropyl aluminum ethoxide, di-isobutyl aluminum ethoxide, methylethyl aluminum ethoxide and mixtures thereof. In one aspect the reducingagent is diethyl aluminum ethoxide (DEAIE).

The non-polar, aprotic solvent may be an alkane, or a mixture ofalkanes, wherein each alkane independently has from 5 to 20 carbonatoms, alternatively from 5 to 12 carbon atoms, alternatively from 5 to10 carbon atoms. Each alkane independently may be acyclic or cyclic.Each acyclic alkane independently may be straight chain or branchedchain. The acyclic alkane may be pentane, 1-methylbutane (isopentane),hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane(isoheptane), octane, nonane, decane, or a mixture of any two or morethereof. The cyclic alkane may be cyclopentane, cyclohexane,cycloheptane, cyclooctane, cyclononane, cyclodecane, methycyclopentane,methylcyclohexane, dimethylcyclopentane, or a mixture of any two or morethereof. The non-polar, aprotic solvent may be a mixture of at least oneacyclic alkane and at least one cyclic alkane.

Thereafter, the slurry of the activated (unsupported or supported)reduced chromium oxide catalyst compound and system may be dried toremove the non-polar, aprotic solvent. The drying comprises heating theslurry, optionally under reduced pressure, and in an environment thatexcludes oxidizing contaminants such as air or oxygen. The dryingprocess transitions the activated (unsupported or supported) reducedchromium oxide catalyst compound and system from a viscous slurry to apartially dried slurry or mud to a free-flowing powder. Helical ribbonagitators may be used in vertical cylindrical blenders to accommodatethe varying mixture viscosities and agitation requirements. Drying maybe conducted at pressures above, below, or at normal atmosphericpressure as long as contaminants such as oxygen are strictly excludedfrom the activated (unsupported or supported) reduced chromium oxidecatalyst compound and system. Drying temperatures may range from 0° to100° C., alternatively from 40° to 85° C., alternatively from 55° to 75°C. Drying times may be from 1 to 48 hours, alternatively from 3 to 26hours, alternatively from 5 to 20 hours. All other things being equal,the higher the drying temperature and/or lower the drying pressure, theshorter the drying time, and vice versa. After drying, the activated(unsupported or supported) reduced chromium oxide catalyst compound andsystem may be stored under an inert atmosphere until use.

Activator. Also referred to as a co-catalyst, an activator is a compoundthat enhances the catalytic performance of a catalyst. Aluminum alkylsmay be used as activators for reduced chromium oxide catalyst compounds.The aluminum alkyl may also be used to improve the performance of theactivated (unsupported or supported) reduced chromium oxide catalystcompound and system. The use of an aluminum alkyl allows for variablecontrol of side branching in the polymer product, and desirable catalystproductivities. The aluminum alkyl may be applied to the reducedchromium oxide catalyst compound directly before the latter is fed intothe GPP reactor. Alternatively, the reduced chromium oxide catalystcompound and aluminum alkyl may be fed separately into the GPP reactor,wherein they contact each other in situ, which may shorten or eliminateany catalyst induction time. See U.S. Pat. No. 7,504,467 B2.

During the inventive method or use, the chromium-based catalyst system,once activated, may be fed into the GPP reactor as a dry powder,alternatively as a slurry in a non-polar, aprotic solvent, which is asdescribed above.

Chromium oxide catalyst compounds and reduced chromium oxide catalystcompounds and methods of preparation thereof, as well as characteristicsof the polymer products formed therefrom, are described in U.S. Pat. No.6,989,344; US 2011/0010938 A1; US 2016/0297907 A1; or WO 2017/132092 A1.

In some embodiments the chromium-based catalyst system comprises thereduced chromium oxide catalyst system. In some embodiments the reducedchromium oxide catalyst system comprises ACCLAIM™ K-100 catalyst system,ACCLAIM™ K-110 catalyst system, or ACCLAIM™ K-120 catalyst system. TheACCLAIM™ catalyst systems are all available from Univation Technologies,LLC, Houston, Tex., USA.

The ACCLAIM™ K-100, K-110, and K-120 catalyst systems may be prepared oncommercial scales as follows. The preparations varying slightlydepending on a small differences in concentrations of aluminum (DEALE)used thereon in Part (B), described herein. Part (A): activation ofsupported chromium oxide catalyst system as a powder. Charge a fluidizedbed heating vessel with a quantity of a porous silica support containingabout 5 wt % chromium acetate (Grade C35300MSF chromium on silica,produced by PQ Corporation), which amounts to about 1 wt % Cr content,having a particle size of about 82 micrometers (μm) and a surface areaof about 500 m²/g. Heat up the vessel contents at a rate of about 50° C.per hour under a dry nitrogen stream up to 200° C., and hold at thattemperature for about 4 hours. Next, further heat up the vessel contentsat a rate of about 50° C. per hour under dry nitrogen to 450° C., andhold at that temperature for about 2 hours. Replace the dry nitrogenstream with a stream of dry air, and heat the vessel contents at a rateof about 50° C. per hour to 600° C., and maintain at 600° C. for about 6hours to give activated chromium oxide catalyst. Cool the activatedcatalyst dry air stream (at ambient temperature) to about 300° C.,replace the dry air stream with a dry nitrogen stream and further coolfrom 300° C. to room temperature under the dry nitrogen stream (atambient temperature). The resulting cooled, activated supported chromiumoxide catalyst system is a powder. Store the powder under dry nitrogenatmosphere in a mixing vessel until used in Part (B).

Part (B) reduction of activated chromium oxide catalyst system to giveACCLAIM™ K-100, K-110, or K-120 catalyst system. For pilot scale, fit avertical catalyst blender with a double helical ribbon agitator, andcharge with about 0.86 kg of the powder form of the activated supportedchromium oxide catalyst of Part (A) under an inert atmosphere. Add driedhexane or isopentane solvent (7.1 L solvent per kg of powder) toadequately suspend the powder and form a slurry. Agitate the slurry,warm to approximately 45° C., and add a 25 wt % solution of DEAIE (AkzoNobel) in isopentane or hexane above the surface of the catalyst slurryat a rate so that the addition occurs over about a 40 minutes timeperiod to obtain a selected wt % aluminum loading on the powder, whereinthe wt % aluminum loading is different depending upon whether ACCLAIM™K-100, K-110, or K-120 catalyst system is being prepared. Furtheragitate the resulting at a controlled rate for about 1 hour on a pilotscale or 2 hours on a commercial scale. Then substantially remove thesolvent from the resulting reaction mixture by drying at a selectedjacket temperature for about 16 to 21 hours. Select the jackettemperature to give a material temperature that lines out near a targetof 61°, 64°, 71°, or 81° C. during the later hours of drying, typically16 hours for pilot scale. As drying time goes on, apply a progressivelystronger vacuum to the vessel. The reduced chromium oxide catalystsystem comprising ACCLAIM™ K-100, K-110, or K-120 catalyst system isobtained as a dry, free-flowing powder, which is stored in a containerunder dry nitrogen pressure until used in a polymerization reaction.

Unimodal ethylene-co-1-butene copolymer

Ethylene. A compound of formula H₂C═CH₂. The polymerizable monomer.

1-butene. A compound of formula H₂C═C(H)CH₂CH₃. The polymerizablecomonomer.

Unimodal ethylene-co-1-butene copolymer. A macromolecule, or collectionof macromolecules, composed of repeat units wherein 50.0 to <100 molepercent (mol %), alternatively 70.0 to 99.99 mol %, alternatively 95.0to 99.9 mol % of such repeat units are derived from ethylene monomer,and from >0 to 50.0 mol %, alternatively from 0.01 to 30.0 mol %,alternatively 0.1 to 5.0 mol % of the remaining repeat units arecomonomeric units derived from 1-butene; or collection of suchmacromolecules. The collection of macromolecules is characterized by asingle peak (no shoulder) in a plot of dW/d Log(MW) on the y-axis versusLog(MW) on the x-axis to give a Gel Permeation Chromatograph (GPC)chromatogram, wherein Log(MW) and dW/d Log(MW) are as defined below andmeasured by Gel Permeation Chromatograph (GPC) Test Method describedherein.

Film

The film. The film may be unembossed or embossed. The film may betailored for specific uses by adjusting thickness of the film,combination with other films or additives, or not. The film may be amonolayer film. In some aspects the film has a thickness from 0.0102 to0.254 mm (0.400 mil to 10 mils), alternatively from 0.01143 mm to 0.254mm (0.450 mil to 10 mils), alternatively from 0.01143 mm to 0.127 mm(0.450 mil to 5.00 mils), alternatively from 0.01143 mm to 0.0762 mm(0.450 mil to 3.00 mils), alternatively from 0.0127 mm to 0.0635 mm(0.500 mil to 2.50 mils).

The film may be made using any extrusion or co-extrusion methodsincluding blown, tentered, and cast film methods. The blown film may bemade on a blown-film-line machine configured for making polyethylenefilms. The machine may be configured with a feed hopper in fluidcommunication with an extruder in heating communication with a heatingdevice capable of heating a polyethylene in the extruder to atemperature of up to 500° C. (e.g., 430° C.), and wherein the extruderis in fluid communication with a die having an inner diameter of 20.3centimeters (8 inches) and a fixed die gap (e.g., 1.778 millimeter gap(70 mils)), a blow up ratio of 2.5:1, and a Frost Line Height (FLH) of76±10 centimeters (30±4 inches) from the die. Step (a) may be done inthe feed hopper.

The film may be unoriented, uniaxially oriented, or biaxially oriented.The film may be oriented in the direction of extrusion (machinedirection or MD), alternatively in the direction transverse to thedirection of extrusion (transverse direction or TD). The film may beoriented by stretching or pulling a film in the MD to give a MD orientedfilm, simultaneously or followed by stretching or pulling the MDoriented film in the TD to give a film that is biaxially oriented in MDand TD.

The film may have one or more improved properties such as enhanced(increased) bubble stability, enhanced (increased) MD and/or TDElmendorf Tear performance, enhanced (increased) MD tensile strengthand/or TD tensile strength, enhanced (increased) dart impactperformance, or a combination of any two or more thereof.

The film may be combined with one or more other film layers to makemultilayer films or laminates.

The film is useful for making containers and wraps that have enhancedpuncture resistance. Examples of such containers are bags such as icebags and grocery bags. Examples of such wraps are stretch films, meatwraps, and food wraps. The inventive copolymer is also useful in avariety of non-film related applications including in vehicle parts.

The following apply unless indicated otherwise. Alternatively precedes adistinct embodiment. ASTM means the standards organization, ASTMInternational, West Conshohocken, Pa., USA. Any comparative example isused for illustration purposes only and shall not be prior art. Free ofor lacks means a complete absence of; alternatively not detectable.IUPAC is International Union of Pure and Applied Chemistry (IUPACSecretariat, Research Triangle Park, N.C., USA). May confers a permittedchoice, not an imperative. Operative means functionally capable oreffective. Optional(ly) means is absent (or excluded), alternatively ispresent (or included). Properties are measured using a standard testmethod and conditions for the measuring (e.g., viscosity: 23° C. and101.3 kPa). Ranges include endpoints, subranges, and whole and/orfractional values subsumed therein, except a range of integers does notinclude fractional values. Room temperature: 23° C.±1° C.

EXAMPLES

Dart Impact Test Method: measured according to ASTM D1709-16a, StandardTest Methods for Impact Resistance of Plastic Film by the Free-FallingDart Test Method, Method A. Method A employs a dart with a 38.10±0.13-mm(1,500±0.005-in.) diameter hemispherical head dropped from a height of0.66±0.01 m (26.0±0.4 in.). This test method can be used for films whoseimpact resistances require masses of about 50 g or less to about 6 kg tofracture them. Results expressed in grams (g).

Density is measured according to ASTM D792-13, Standard Test Methods forDensity and Specific Gravity (Relative Density) of Plastics byDisplacement, Method B (for testing solid plastics in liquids other thanwater, e.g., in liquid 2-propanol). Report results in units of grams percubic centimeter (g/cm³). In some aspects the density is from 0.89 to0.98 g/cm³, alternatively from 0.92 to 0.97 g/cm³, alternatively 0.940to 0.960 g/cm³.

Dynamic Mechanical Analysis (DMA) Test Method: a dynamic mechanicalanalysis method measured at 190° C. and 0.126 radians per second (rad/s)or 126 rad/s using the following procedure: Perform small-strain (10%)oscillatory shear measurements on polymer melts at 190° C. using anARES-G2 Advanced Rheometric Expansion System, from TA Instruments, withparallel-plate geometry to obtain the values of storage modulus (G′),loss modulus (G″) complex modulus (G*) and complex viscosity (η*) as afunction of frequency (ω). Obtain a SH1000 value by calculating thecomplex viscosities (η*) at given values of frequency (ω), andcalculating the ratio of the two viscosities. For example, using thevalues of frequency (ω) of 0.126 rad/s and 126 rad/s, obtain theSH1000=Eta0.126/Eta126 (i.e., η*(0.126 rad/s)/η*(126 rad/s) at aconstant value of loss modulus G″ of 3,000 pascals (Pa). The SH1000 isdefined as the ratio of the two complex viscosities Eta0.126/Eta126(i.e., η*(0.126 rad/s)/η*(126 rad/s).

Elmendorf Tear Test Method: measured according to ASTM D1922-09,Standard Test Methods for Propagation Tear Resistance of Plastic Filmand Thin Sheeting by Pendulum Method, Type B (constant radius).(Technically equivalent to ISO 6383-2.) Report results as normalizedtear in cross direction (CD) or machine direction (MD) in gram-force(gf).

Film Puncture Test Method: ASTM D5748-95(2012), Standard Test Method forProtrusion Puncture Resistance of Stretch Wrap Film. Determines theresistance to puncture of a film as resistance to penetration of thefilm by a probe impinging the film at a standard speed such as 250millimeters per minute (mm/min.). The probe is coated with apolytetrafluoroethylene and has an outer diameter of 1.905 cm (0.75inch). The film is clamped during the test. The probe eventuallypenetrates or breaks the clamped film. The peak force at break, i.e.,the maximum force, energy (work) to break or penetrate the clamped film,and the distance that the probe has penetrated at break, are recordedusing mechanical testing software. The probe imparts a biaxial stress tothe clamped film that is representative of the type of stressencountered by films in many product end-use applications. Thisresistance is a measure of the energy-absorbing ability of a film toresist puncture under these conditions.

Gel permeation chromatography (GPC) Test Method: Weight-AverageMolecular Weight Test Method: determine M_(w), number-average molecularweight (M_(n)), and M_(w)/M_(n) using chromatograms obtained on a HighTemperature Gel Permeation Chromatography instrument (HTGPC, PolymerLaboratories). The HTGPC is equipped with transfer lines, a differentialrefractive index detector (DRI), and three Polymer Laboratories PLgel 10μm Mixed-B columns, all contained in an oven maintained at 160° C.Method uses a solvent composed of BHT-treated TCB at nominal flow rateof 1.0 milliliter per minute (mL/min.) and a nominal injection volume of300 microliters (μL). Prepare the solvent by dissolving 6 grams ofbutylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagentgrade 1,2,4-trichlorobenzene (TCB), and filtering the resulting solutionthrough a 0.1 micrometer (μm) Teflon filter to give the solvent. Degasthe solvent with an inline degasser before it enters the HTGPCinstrument. Calibrate the columns with a series of monodispersedpolystyrene (PS) standards. Separately, prepare known concentrations oftest polymer dissolved in solvent by heating known amounts thereof inknown volumes of solvent at 160° C. with continuous shaking for 2 hoursto give solutions. (Measure all quantities gravimetrically.) Targetsolution concentrations, c, of test polymer of from 0.5 to 2.0milligrams polymer per milliliter solution (mg/mL), with lowerconcentrations, c, being used for higher molecular weight polymers.Prior to running each sample, purge the DRI detector. Then increase flowrate in the apparatus to 1.0 mL/min/, and allow the DRI detector tostabilize for 8 hours before injecting the first sample. Calculate M_(w)and M_(n) using universal calibration relationships with the columncalibrations. Calculate MW at each elution volume with followingequation:

${{\log M_{X}} = {\frac{\log \left( {K_{X}/K_{PS}} \right)}{a_{X} + 1} + {\frac{a_{PS} + 1}{a_{X} + 1}\log M_{PS}}}},$

where subscript “X” stands for the test sample, subscript “PS” standsfor PS standards, a_(PS)=0.67, K_(PS)=0.000175, and a_(x) and K_(x) areobtained from published literature. For polyethylenes,a_(x)/K_(x)=0.695/0.000579. For polypropylenesa_(x)/K_(x)=0.705/0.0002288. At each point in the resultingchromatogram, calculate concentration, c, from a baseline-subtracted DRIsignal, I_(DRI), using the following equation: c=K_(DRI)I_(DRI)/(dn/dc),wherein K_(DRI) is a constant determined by calibrating the DRI, /indicates division, and dn/dc is the refractive index increment for thepolymer. For polyethylene, dn/dc=0.109. Calculate mass recovery ofpolymer from the ratio of the integrated area of the chromatogram ofconcentration chromatography over elution volume and the injection masswhich is equal to the pre-determined concentration multiplied byinjection loop volume. Report all molecular weights in grams per mole(g/mol) unless otherwise noted. Further details regarding methods ofdetermining Mw, Mn, MWD are described in US 2006/0173123 page 24-25,paragraphs [0334] to [0341]. Plot of dW/d Log(MW) on the y-axis versusLog(MW) on the x-axis to give a GPC chromatogram, wherein Log(MW) anddW/d Log(MW) are as defined above.

High Load Melt Index (HLMI) I₂₁ Test Method: use ASTM D1238-13, StandardTest Method for Melt Flow Rates of Thermoplastics by ExtrusionPlatometer, using conditions of 190° C./21.6 kilograms (kg). Reportresults in units of grams eluted per 10 minutes (g/10 min.).

Melt Index (“I₂”) Test Method: for ethylene-based (co)polymer ismeasured according to ASTM D1238-13, using conditions of 190° C./2.16kg, formerly known as “Condition E” and also known as I₂.

Melt Index I₅ (“I₅”) Test Method: use ASTM D1238-13, using conditions of190° C./5.0 kg. Report results in units of grams eluted per 10 minutes(g/10 min.).

Melt Flow Ratio MFR5:(“I₂₁/I₅”) Test Method: calculated by dividing thevalue from the HLMI I₂₁ Test Method by the value from the Melt Index I₅Test Method.

Melt Storage Modulus Test Method: On polymer melts at 190° C. performsmall-strain (10%) oscillatory shear at varying frequency from 0.02radian per second (rad/s) to about 200 rad/s using an ARES-G2 AdvancedRheometric Expansion System, from TA Instruments, with parallel-plategeometry to obtain the G′ (G″=3,000 Pa) value in pascals of melt storagemodulus (G′) at a dynamic frequency where loss modulus (G″) is equal to3,000 Pa.

Optical Gloss Test Method: ASTM D2457-13, Standard Test Method forSpecular Gloss of Plastic Films and Solid Plastics. Measure speculargloss using a glassometer at incident angles 20°, 45°, 60°, or 75°.Specular gloss is unitless.

Optical Haze Test Method: D1003-13, Standard Test Method for Haze andLuminous Transmittance of Transparent Plastics. Measure haze using ahazemeter. Express haze as percentage of luminous transmission which inpassing through the film deviates from an incident beam by forwardscattering.

1% or 2% Secant Modulus Test Method: measured according to ASTM D882-12,Standard Test Methods for Tensile Properties of Thin Plastic Sheeting.Used either 1% or 2% secant modulus in cross direction (CD) or machinedirection (MD). Report results in megapascals (MPa). 1,000.0 pounds persquare inch (psi)=6.8948 MPa.

Tensile Modulus Test Method: measured according to ASTM D882-12,Standard Test Methods for Tensile Properties of Thin Plastic Sheeting.Report results in cross direction (CD) as average strain at yield inpercent (%) or average stress at yield in megapascals (MPa), or inmachine direction (MD) as average strain at yield in percent (%).1,000.0 pounds per square inch (psi)=6.8948 MPa.

Antioxidant 1: pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Obtained asIRGANOX 1010 from BASF.

Antioxidant 2: tris(2,4-di-tert-butylphenyl)phosphite. Obtained asIRGAFOS 168 from BASF.

Catalyst Neutralizer 1: calcium stearate.

Catalyst Neutralizer 2: zinc stearate.

Chromium-based Catalyst system: the ACCLAIM™ K-100 catalyst system.

Obtained from Univation Technologies LLC, Houston, Tex., USA.

Comonomer: 1-butene. See later for C₄/C₂ gas molar ratio.

Ethylene (“C₂”): See later for partial pressure of C₂.

Molecular hydrogen gas (“H₂”): See later for H₂/C₂ gas molar ratio.

Molecular oxygen gas (“O₂”): See later for O₂/C₂ gas volume ratio.

Unimodal ethylene-co-1-butene copolymers: target density is 0.948 to0.950 g/cm³ and target flow index (I₂₁) is 15 to 19 g/10 minutes.

Inventive Examples 1 to 5 (IE1 to IE5): polymerization procedure: Runsbegan with ACCLAIM™ K-100 Catalyst and comonomer 1-butene according tothe Pilot Reactor and method described earlier to give in differentparts, as described below, different embodiments of the unimodalethylene-co-1-butene copolymer as granular resins. The operatingconditions for the polymerization are reported below in Table 1.

TABLE 1 Operating conditions for IE1 to IE5. IE1 IE2 IE3 IE4 IE5 PARTNo. 1 3 4 5 5-6 Reactor Type S, CM, PP, S, CM, PP, S, CM, PP, S, CM, PP,S, CM, PP, FB GPP* FB GPP FB GPP FB GPP FB GPP Reactor Purging gasAnhydrous Anhydrous Anhydrous Anhydrous Anhydrous N₂ N₂ N₂ N₂ N₂ BedTemp. (° C.) 102.0 105.0 105.0 110.0 110.0 Rx Pressure(kpa)^({circumflex over ( )}) 2501.9 2501.8 2502.7 2503.6 2501.7 C₂Partial Pressure (kpa) 1378.9 1377.8 1378.8 1377.2 1379.6 H₂/C₂ MolarRatio 0.102 0.057 0.102 0.102 0.057 C₄/C₂ Molar Ratio 0.0201 0.02000.0190 0.0151 0.0160 O₂/C₂ Volume Ratio (ppbv) 66.4 75.1 55.0 35.5 50.6Induced Condensing Agent None None None None None Superficial GasVelocity 0.52 0.53 0.54 0.54 0.52 (m/sec) Unimodal Catalyst SystemACCLAIM ™ ACCLAIM ™ ACCLAIM ™ ACCLAIM ™ ACCLAIM ™ K-100 K-100 K-100K-100 K-100 Catalyst loading (Cr, wt %) 0.843 0.843 0.843 0.843 0.843Catalyst loading (Al, wt %) 1.392 1.392 1.392 1.392 1.392 Startingseedbed = granular Preloaded Preloaded Preloaded Preloaded PreloadedHDPE resin in reactor in reactor in reactor in reactor in reactorStarting Bed Weight (kg) 42.6 39.6 43.4 45.5 43.0 Copolymer ProductionRate 18.2 16.3 18.0 18.3 17.4 (kg/hour) Copolymer Residence Time 2.352.42 2.41 2.49 2.47 (hour) Copolymer Fluid Bulk 214.7 209.9 222.3 235.5221.9 Density, Comp. (kg/m³) *S, CM, PP, FB, GPP: single, continuousmode, pilot plant, fluidized bed gas phase polymerization. {circumflexover ( )}Rx Pressure (kPa): reactor total pressure in kilopascals.

As shown in Table 1, the operating conditions used to make the unimodalethylene-co-1-butene copolymers of IE1 to IE5 comprise a bed temperaturefrom 102.0° to 110.0° C.; an ethylene (O₂) partial pressure from 1377 to1380 kpa; an H₂/C₂ Molar Ratio from 0.057 to 0.102; a C₄/C₂ Molar Ratiofrom 0.0151 to 0.0201; an O₂/C₂ Volume Ratio from 35.5 to 75.1 ppbv(parts per billion by volume/volume); and a superficial gas velocityfrom 0.52 to 0.54 m/sec (meter per second). In certain embodiments, themethod of synthesizing the unimodal ethylene-co-1-butene copolymeremploy the aforementioned operating conditions.

Formulation and Pelletization Procedure: Each of the different granularresins of IE1 to IE5 was separately mixed with 1,300 parts per millionweight/weight (ppm) of Antioxidant 1, 1,300 ppm Antioxidant 2, 1,500 ppmCatalyst Neutralizer 1, and 700 ppm Catalyst Neutralizer 2 in a ribbonblender, and then compounded into strand cut pellets using a twin-screwextruder ZSK40. The resulting pellets of each resin were tested for flowindex (I₂₁), density, and melt storage modulus G′ (G″=3,000 Pa)according to their aforementioned respective test methods. Results arereported later. In certain embodiments, the unimodalethylene-co-1-butene copolymer further comprises at least oneantioxidant selected from Antioxidants 1 and 2; at least one catalystneutralizer selected from Catalyst Neutralizers 1 and 2; or acombination thereof. Results are reported below in Table 2.

TABLE 2 Melt properties of IE1 to IE5. Test IE1 IE2 IE3 IE4 IE5 I₂₁(190° C., 21.6 kg) 16.4 16.5 14.8 15.5 18.7 (g/10 min.) MFR5 (I₂₁/I₅)26.0 24.8 24.5 22.0 20.7 melt elasticity G′ 2236 2192 2139 1974 1990 (G″= 3,000 Pa) (Pa) Eq. 1 met? Yes Yes Yes Yes Yes Shear thinning SH100047.5 44.4 44.9 39.1 35.9 Eq. 2 met? Yes Yes Yes Yes Yes

As shown in Table 2, the melt properties of the unimodalethylene-co-1-butene copolymers of IE1 to IE5 comprise a high-load meltindex I₂₁ (190° C., 21.6 kg) from 14.8 to 18.7 g/10 min.; a melt flowratio MFR5 (I₂₁/I₅) from 20.7 to 26.0; a melt elasticity G′ (G″=3,000Pa) from 1974 to 2236 Pa; a shear thinning SH1000 from 35.9 to 47.5; andsatisfaction of each of Equations 1 and 2.). In certain embodiments, theunimodal ethylene-co-1-butene copolymer is characterized by any one,alternatively all but one, alternatively each of the aforementioned meltproperties.

The melt properties data in Table 2 for the unimodalethylene-co-1-butene copolymer were analyzed to discover on whatreactor/process operating conditions the melt properties depend. Thefollowing operating conditions are found to influence the meltproperties of the unimodal ethylene-co-1-butene copolymer made thereby:increasing H₂/O₂ gas molar ratio and reactor bed temperature in theprocess yielded inventive unimodal ethylene-co-1-butene copolymerbeneficially having improved (reduced) shear thinning and lower meltelasticity G′ (G″=3,000 Pa) (Pa), and thus having improved (increased)bubble stability in blown film process.

Granular resins of IE1 to IE5 were characterized by density, molecularweights, molecular mass dispersity (M_(w)/M_(n)), Øm, I₅, I₂₁. Resultsare reported below in Table 3.

TABLE 3 Resin properties of IE1 to IE5. Test IE1 IE2 IE3 IE4 IE5 Density(g/cm³) 0.949 0.949 0.949 0.949 0.949 M_(n) (g/mol) 12,196 11,955 12,02012,783 12,860 M_(w) (g/mol) 303,745 309,455 278,978 309,879 263,745M_(w)/M_(n) (Ð_(M)) 24.91 25.89 23.21 24.24 20.51 M_(z) (g/mol)3,579,743 3,736,107 2,438,342 3,797,848 2,425,366

As shown in Table 3, the resin properties of the unimodalethylene-co-1-butene copolymers of IE1 to IE5 comprise a density of0.949 g/cm³; a number-average molecular weight from 11,955 to 12,860g/mol; a weight-average molecular weight from 263,745 to 309,879 g/mol;a molecular mass dispersity M_(w)/M_(n) (Ø_(M)) from 20.51 to 25.89; anda z-average molecular weight from 2,425,366 to 3,797,848 g/mol. Incertain embodiments, the unimodal ethylene-co-1-butene copolymer ischaracterized by any one, alternatively all but one, alternatively eachof the aforementioned resin properties.

Film Forming Procedure: Pellets of granular resins of the unimodalethylene-co-1-butene copolymer of IE1 to IE5 are separately melted atmelt temperature described herein, and separately blown into films usingan Alpine 50 millimeter (mm) 25:1 length to diameter (L/D) dimensionedbarrier single screw extruder, a 120 mm inner diameter die, a 1.2 mm diegap, without IBC (internal bubble cooling). The bubble stabilities ofthe films were measured according to the following method: (a) bubblerating at standard output rate of 6.9 kilograms per hour-centimeter(kg/hour-cm, bubble rating STD); (b) a bubble rating at standard outputrate with maximum line speed greater than 14.2 meters per minute(m/min., bubble rating MLS); and (c) bubble rating at maximum outputrate (20% or more output rate, bubble rating MOR). Bubble ratings werescored on a scale from 1 to 5 as follows: 1. Film could not be made. 2.Film could be made but production of film had bubble instability. 3.Film could be made but production of film had slight bubble instability.4. Film could be made with bubble stability. 5. Film could be made withvery stable bubble. If the bubble rating is 4 or 5, the resin passes thebubble stability test and is characterized as “Good”. If the bubblerating is 3, the resin passes the bubble stability test and ischaracterized as “Okay”. If the bubble rating is 2, the resin fails thebubble stability test and is characterized as “Moderate”. If the bubblerating is 1, the resin fails the bubble stability test and ischaracterized as “Poor”. Also, dart impact and Elmendorf tear weremeasured on films having a thickness of 0.0127 millimeter (mm)=12.7micrometer (μm) and according to the aforementioned test methods. Filmresults are reported below in Table 4.

TABLE 4 Film properties of IE1 to IE5. Test IE1 IE2 IE3 IE4 IE5 Extruderspeed (rpm) 94 94 94 94 94 Motor load (%) 63.3 63.5 63.7 64.6 61.7 melttemp. (° C.) 196.3 194.2 195.8 193.9 197.3 Die Press (MPa) 36.4 35.137.6 38.9 36.4 Bubble Rating STD Good Good Good Good Good Bubble RatingMLS Good Good Good Good Good Bubble Rating MOR Good Good Good Good OkayAvg. Tear CD (gf) 46 64 63 155 150 Avg. Tear MD (gf) 22 19 18 16 13 DartImpact (g) 123 131 126 135 119

As shown in Table 4, the film properties of the blown films of theunimodal ethylene-co-1-butene copolymers of IE1 to IE5 comprise a bubblerating STD of Good, a bubble rating MLS of Good, a bubble rating MOR ofGood or okay, an average Elmendorf Tear in cross-direction (CD) from 46to 155 gf, an average Elmendorf tear in machine direction (MD) from 13to 22 gf, and a dart impact from 119 to 135 g. In certain embodiments,the unimodal ethylene-co-1-butene copolymer, and the blown filmsthereof, are independently characterized by any one, alternatively allbut one, alternatively each of the aforementioned film properties.

Prophetic Characterizations: The unimodal ethylene-co-1-butenecopolymers of IE1 to IE5 may be further characterized by any one or moreof the Melt Index (“I₂”) Test Method, 1% or 2% Secant Modulus TestMethod, and Tensile Modulus Test Method. The films made from theunimodal ethylene-co-1-butene copolymers of IE1 to IE5 may be furthercharacterized by any one or more of the Film Puncture Test Method,Optical Gloss Test Method, and Optical Haze Test Method.

1. A unimodal ethylene-co-1-butene copolymer that, when in melted form at 190° C., is characterized by a melt property space defined by a combination of shear thinning and melt elasticity properties, wherein the shear thinning property is defined according to equation 1 (Eq. 1): G′ (G″=3,000 Pa)<66.6*MFR5+630 (Eq. 1); and the melt elasticity property is defined according to equation 2 (Eq. 2): G′ (G″=3,000 Pa)<23.5*SH1000+1182 (Eq. 2); wherein < is less than; * is multiplication; / is division; = is equals; G′ (G″=3,000 Pa) is melt elasticity in Pascals (Pa) measured according to Melt Storage Modulus Test Method at loss modulus G″=3000 pascals; MFR5 is melt flow ratio I₂₁/I₅; I₂₁ is high-load melt index (HLMI) in grams per 10 minutes (g/10 min) measured according to ASTM D1238-13 (190° C., 21.6 kg); I₅ is melt index in g/10 min measured according to ASTM D1238-13 (190° C., 5.0 kg); SH1000=Eta0.126/Eta126; Eta0.126 is complex viscosity in Pascal-seconds (Pa-s) measured at 0.126 radian per second (rad/s) by Dynamic Mechanical Analysis Test Method; and Eta126 is complex viscosity Pa-s measured at 126 rad/s by the Dynamic Mechanical Analysis Test Method.
 2. The unimodal ethylene-co-1-butene copolymer of claim 1 wherein the melt property space is further defined by any one of limitations (i) to (xii): (i) an I₂₁ from 13.0 to 25.0 g/10 min., measured according to ASTM D1238-13 (190° C., 21.6 kg); (ii) a MFR5 (“I₂₁/I₅”) from 20.0 to 27.0, measured according to ASTM D1238-13 (190° C., 21.6 kg, “I₂₁”; and 190° C., 5.0 kg, “I₅”); (iii) an SH1000 from 35.0 to 49.0, measured by the Dynamic Mechanical Analysis Test Method; (iv) a melt storage modulus G′ (G″=3,000 Pa) value from 1900 to 2300 Pa, measured according to the Melt Storage Modulus Test Method; (v) both (i) and (ii); (vi) both (i) and (iii); (vii) both (i) and (iv); (viii) both (ii) and (iii); (ix) both (ii) and (iv); (x) both (iii) and (iv); (xi) any three of (i) to (iv); and (xii) each of (i) to (iv).
 3. The unimodal ethylene-co-1-butene copolymer of claim 1 characterized by any one of limitations (i) to (xvii): (i) a density from 0.9410 to 0.9550 gram per cubic centimeter (g/cm³), measured according to ASTM D792-13, Method B; (ii) a weight-average molecular weight (M_(w)) from 200,000.0 to 400,000.0 grams per mole (g/mol), measured according to the Gel Permeation Chromatography (GPC) Test Method; (iii) a number-average molecular weight (M_(n)) from 11,000.0 to 14,000.0 g/mol, measured according to the GPC Test Method; (iv) a z-average molecular weight (M_(t)) from 2,400,000 to 3,600,000 g/mol, measured according to the GPC Test Method; (v) a molecular mass dispersity (M_(w)/M_(n)), Ø_(M), from 20.0 to 26.0, wherein M_(w) and M_(n) are measured according to the GPC Test Method; (vi) both (i) and (ii); (vii) both (i) and (iii); (viii) both (i) and (iv); (ix) both (i) and (v); (x) both (ii) and (iii); (xi) both (ii) and (iv); (xii) both (ii) and (v); (xiii) both (iii) and (iv); (xiv) both (iii) and (v); (xv) both (iv) and (v); (xvi) any four of (i) to (v); and (xvii) each of (i) to (v).
 4. The unimodal ethylene-co-1-butene copolymer of claim 1 that, when in the form of a blown film and having a thickness of 0.0127 millimeter (mm, 0.500 mil), is characterized by any one of limitations (i) to (xii): (i) a dart impact from 115 to 139 grams (g), measured according to the Dart Impact Test Method; (ii) an Elmendorf tear in cross direction (CD) from 40.0 to 160.0 gram-force (gf), measured according to the Elmendorf Tear Test Method; (iii) an Elmendorf tear in machine direction (MD) from 10.0 to 250.0 gf, measured according to the Elmendorf Tear Test Method; (iv) a bubble stability rating of Good, measured according to the Bubble Stability Test Method; (v) both (i) and (ii); (vi) both (i) and (iii); (vii) both (i) and (iv); (viii) both (ii) and (iii); (ix) both (ii) and (iv); (x) both (iii) and (iv); (xi) any two of (i) to (iii); and (xii) each of (i) to (iii).
 5. A method of synthesizing the unimodal ethylene-co-1-butene copolymer of claim 1, the method consisting essentially of contacting ethylene and 1-butene with a single catalyst system consisting of a unimodal chromium catalyst system in a single fluidized bed, gas-phase polymerization (FB-GPP) reactor under effective operating conditions comprising a reactor bed temperature (RBT), an average polymer residence time (avgPRT), and an ethylene partial pressure (C2P) and receiving an ethylene (C₂) feed, a comonomer (C₄) feed, a hydrogen (H₂) feed, and, optionally, an oxygen (O₂) feed wherein the feeds are characterized by a H₂/C₂ gas molar ratio (H₂/C₂), a comonomer/ethylene gas molar ratio (“C₄/C₂”), and a O₂/C₂ gas volume ratio (“[O₂/C₂]”, vol/vol in ppmv); wherein RBT is from 101° to 111° C.; avgPRT is from 1.70 to 3.10 hours, C2P is from 1,100 to 1,900 kilopascals (kPa); H₂/C₂ gas molar ratio is from 0.01 to 0.110; C₄/C₂ gas molar ratio is from 0.010 to 0.021; and O₂/C₂ gas volume ratio is from >0 to 90 parts per billion volume/volume (ppbv); thereby synthesizing the unimodal ethylene-co-1-butene copolymer in the FB-GPP reactor.
 6. The method of claim 5 further comprising removing the unimodal ethylene-co-1-butene copolymer from the FB-GPP reactor to give a removed unimodal ethylene-co-1-butene copolymer.
 7. A manufactured article comprising the unimodal ethylene-co-1-butene copolymer of claim
 1. 8. A film consisting essentially of the unimodal ethylene-co-1-butene copolymer of claim
 1. 9. A method of making a blown film, the method comprising melting the unimodal ethylene-co-1-butene copolymer of claim 1 so as to give a melt thereof, extruding the melt through a die configured for forming a bubble so as to make a bubble of the unimodal ethylene-co-1-butene copolymer, and blowing the bubble with a film-blowing machine, thereby making the blown film.
 10. A blown film made by the method of claim 9 and consisting essentially of the unimodal ethylene-co-1-butene copolymer. 